Process for producing reaction product of 1,3-conjugated diene compound and compound having terminal vinyl group and catalyst used therefor

ABSTRACT

A REACTION PRODUCT OF 1,3-CONJUGATED DIENE COMPOUND AND A COMPOUND HAVING A TERMINAL VINYL GROUP IS PRODUCED IN THE PRESENCE OF A CATALYST PREPARED BY REACTING (1) A P PALLADIUM COMPOUND, (2) A COMPOUND HAVING AN ANION SELECTED FROM TETRA- AND HEXAFLUORO-COMPLEX ANION AND PERCHLORATE ANION AND (3) A PHOSPHOROUS COMPOUND SELECTED FROM A TERTIARY PHOSPHINE AND A TERTIARY PHOSPHITE. WHEN THE COMPOUND HAVING A TERMINAL VINYL GROUP IS THE SAME AS THE 1,3-CONJUGATED DIENE COMPOUND, AN OLIGOMER OF 1,3- CONJUGATED DIENE COMPOUND IS PRODUCED. ON THE OTHER HAND, WHEN THE TWO COMPOUNDS ARE DIFFERENT, A CO-OLIGOMER OF SAID TWO COMPOUND IS PRODUCED. WHEN THE PHOSPHOROUS COMPOUND IS NOT USED OR THE PHOSPHOROUS COMPOUND IS OTHER THAN PHOSPHOROUS COMPOUND HAVING AT LEAST TO SATURATED HYDROCARBON GROUPS, AN ALCOHOL ADDUCT OF SAID OLIGOMER CAN BE PRODUCED WHEN THE REACTION IS IN THE PRESENCE OF AN ALCOHOL.

United States Patent Oflice 3,792,101 PROCESS FOR PRODUCING REACTIONPRODUCT OF 1,3-CONJUGATED DIENE COMPOUND AND COMPOUND HAVING TEAL VDYYLGROUP AND CATALYST USED THEREFOR Saburo Hattori and Kengo Tatsuoka,Tokyo, Japan, as-

;ignors to Mitsubishi Chemical Industries, Ltd., Tokyo,

apan No Drawing. Filed Feb. 3, 1971, Ser. No. 112,433 Claims priority,application Japan, Feb. 9, 1970,

IS/11,298; Mar. 19, 1970, 45/231,363; Mar. 20, I 1970, 45/215,660; May30, 1970, 45/ 16,524 Int. Cl. C07c 11/00 US. Cl. 260-677 R 16 ClaimsABSTRACT OF THE DISCLOSURE A reaction product of 1,3-conjugated dienecompound and a compound having a terminal vinyl group is produced in thepresence of a catalyst prepared by reacting (1) a palladium compound,(2) a compound having an anion selected from tetraand hexafluoro-complexanion and perchlorate anion and (3) a phosphorous compound selected froma tertiary phosphine and a tertiary phosphite. When the compound havinga terminal vinyl group is the same as the 1,3-conjugated diene compound,an oligomer of 1,3-conjugated diene compound is produced. On the otherhand, when the two compounds are different, a co-oligomer of said twocompounds is produced. When the phosphorous compound is not used or thephosphorous compound is other than phosphorous compound having at leasttwo saturated hydrocarbon groups, an alcohol adduct of said oligomer canbe produced when the reaction is in the presence of an alcohol.

BACKGROUND OF THE INVENTION Field of the invention This inventionrelates to a process for producing a reaction product of a1,3-conjugated diene compound and a compound having a terminal vinylgroup.

Description of the prior art Addition reactions of a 1,3-conjugateddiene compound and an a-olefin compound are known and also homooligomerreactions of a 1, 3-conjugated diene compound, such as butadiene orisoprene are known. It has been known to use Ni-Al type catalysts,Fe-Co-Al type catalysts and Pd-Al type catalysts for the additionreaction of a 1,3-conjugated diene compound and an a-olefin compound. Ithas also been known that Pd-P type catalysts, such as his(triphenylphosphine) (maleic anhydride pallapine) p-benzoquinone(palladium): (C H P] Pd(C H O),

are effective catalysts for producing oligomers of 1,3-

butadiene, such as the chain dimer of butadiene.

SUMMARY OF THE INVENTION An object of this invention is to provide anovel catalyst which is effective for producing a reaction product froma 1,3-conjugated diene compound and a compound having a terminal vinylgroup.

Another object of this invention is to provide a process for producing areaction product from a 1,3-conjugated diene compound and a compoundhaving a terminal vinyl group by using a novel catalyst.

Another object of this invention is to provide a process for producingan oligomer such as a chain dimer, trimer, etc. of a 1,3-conjugateddiene compound by oligomerizing a 1,3-conjugated diene compound in thepresence of the novel catalyst.

3,792,101 Patented Feb- 12, 1974 Still another object of this inventionis to provide a process for producing a co-dimer by reacting a1,3-conjugated diene compound with a non-(conjugated diene) type vinylcompound in the presence of the novel catalyst.

A further object of this invention is to provide a process for producingan alcohol adduct of an oligomer such as a chain dimer, trimer, etc. ofa 1,3-conjugated diene compound by oligomerizing a 1,3-conjugated dienecompound in the presence of an alcohol and the novel catalyst.

These and other objects have now herein been attained by the use of acatalyst prepared by reacting (1) a palladium compound, (2) a compoundhaving tetraor hexa-fluoro-complex anion or perchlorate anion and (3) atertiary phosphine or phosphite, which has been found to be effectivefor the addition reaction of a 1,3-conjugated diene compound and acompound having a terminal vinyl group.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The 1,3-conjugated dienecompound used in the process of thls invention refers to compoundshaving the General Formula 1:

wherein each R is the same or different and each represents hydrogen,halogen or an alkyl group; R represents hydrogen, alkyl group or alkenylgroup.

The typical examples of said 1,3-conjugated diene compound having theformula (1) include butadiene, isoprene, chloroprene, 1,3-pentadiene,1,3,6-n-octatriene, 1, 3,7-n-octatriene, 1,3, 6,10 n dodecatetraene.Especially good results are obtainable with butadiene.

The compound having a terminal vinyl group refers to compounds havingthe General Formula 2,

Rs CH3=$H (2) wherein 'R represents hydrogen, alkyl group, a substitutedor unsubstituted alkenyl group, a substituted or unsubstituted arylgroup, an acyloxy group or an alkoxycarbonyl group.

Typical examples of said compound having a terminal vinyl group includea-olefins compounds, such as ethylene, propylene, butene, pentene,hexene; dienes, such as butadiene, isoprene, 1-acetoxy-2,7-octadiene,lmethoxy-2,7 octadiene; vinyl aromatics, such as styrene; and esters,such as methyl acrylate, ethyl acrylate, vinyl acetate.

When the 1,3-c0njugated diene compound having the Formula 1 is reactedwith a compound having a terminal vinyl group and having the Formula 2in accordance with the process of this invention, the following reactionprodr 3 Other isomers having a double bond in a different position canbe produced instead of said co-dimers.

When said compound having a terminal vinyl group is the same as said1,3-conjugated diene compound, the dimer and trimer of the dienecompound can be produced. However, the dimer and trimer of the1,3-conjugated diene compound are sometimes produced together with saidco-dimer of Formulas 3, 4, 5, 6, and isomerse thereof, even though saidcompound having the terminal vinyl group is dilferent from saidl,3-conjugated diene compound.

The catalyst used in the process of this invention is prepared byreacting (1) the palladium compound, (2) the compound having tetraorhexa-fluoro-complex anion or perchlorate anion and (3) the tertiaryphosphine or tertiary phosphite.

The palladium compound can be various palladium compounds such asorganic salts, inorganic salts, complex salts and vr-allyl typecompounds of palladium. Included are the organic salts, such aspalladium acetate: Pd(OCOCH palladium propionate: Pd(OCO H palladiumbenzoate: Pd(OCOC H halides, such as palladium chloride: PdCl palladiumbromide: PdBr palladium iodide: PdI intermolecular complexes, such aspalladium acetylacetonate: Pd(C H O palladium halide complex havingneutral ligands, such as bis(benzonitrile palladium chloride Pd(C H CN)Cl bis(acetonitrile) palladium chloride Pd(CH CN) Clbis(dimethylformamide) palladium chloride Pd [HCON(CH 01bis(dimethylacetoamide) palladium chloride 3 3)z]2 2,bis(dimethylsulfoxide) palladium chloride s)z]z z;

1r-allyl palladium chloride: (1rC H PdCl) vr-methallyl palladiumchloride: (1r-C H PdCl) l-methyl-vr-allyl palladium chloride:

1,3-trimethyle-1r-allyl palladium chloride; butylene-w-allyl palladiumchloride:

It is especially preferable to use a palladium halide complex having aneutral ligand or a 1r-allyl type palladium halide. The compound havingfiouro-complex anion or perchlorate anion used for the preparation ofthe catalyst can be a salt of a suitable cation and a tetrafluoroborateanion-or a hexafiuoro-sllicate, phosphate, arsenate, antimonate orstannate anion or perchlorate anion. It is preferable to use a metalsalt, especially a silver salt such as AgBF Ag SiF AgPF AgAsF AgClO etc.

It is also possible to use HBF H SiF etc. When said acid is used, it ispreferable to use the palladium compound having an acyloxy group or anacetylacetonate group, such as palladium acetate, 1r-allyl palladiumacetate and palladium acetylacetonate.

The tertiary phosphine or tertiary phosphite used in the preparation ofthe catalyst is a phosphine having the general formula PRRR"' or aphosphite having the general formula P (OR) (OR) (OR"') wherein R, R"and R' are the same or different from each other and represent an alkylgroup, a cycloalkyl group or an aryl group.

The typical tertiary phosphines include triethylphosphine,triisopropylphosphine, tri-n-butylphosphine, tri-n- 1-methyl-3-octylphosphine, tricyclohexylphosphine, triphenylphosphine,tri-p-toluylphosphine and monophenyl-di-n-butylphosphine anddiphenyl-mono-n-butylphosphine. The typical tertiary phosphites includetriethylphosphite tri-nbutylphosphite and triphenylphosphite.

The catalyst can be prepared by adding said components, without limitingthe order of addition. The catalyst can be prepared by reacting (1) thepalladium compound with (2) the compound having tetraorhexa-fluoro-complex anion or perchlorate anion, and then adding (3) thetertiary phosphine or tertiary phosphite. It is also possible to preparethe catalyst by mixing (1) the palladium compound and (3) the tertiaryphosphine or tertiary phosphite and then reacting the mixture with (2)the compound having tetraor hexa-fluoro-complex anion or perchlorateanion. It is also possible to feed the three components 1) (2) (3),respectively, to an autoclave. Sometimes, butadiene is added for thepreparation of the catalyst to stabilize the catalyst. It is usual touse an equivalent molar amount of said palladium compound and saidcompound having tetraor hexa-fluoro-complex anion or perchlorate anion.

It is usual to use 0.12 gram equivalent, preferably 1 gram equivalent ofsaid tertiary phosphine or tertiary phosphite to 1 gram equivalent ofthe palladium.

The prepared catalyst will contain a cationic palladium ion as a cation,and a tetrafluoroborate anion, hexafluoro silicate, phosphate arsenate,antimonate or stannate anion or pherchlorate anion. For example, 1 moleof 1rallyl palladium chloride is reacted with 2 moles of silverfluoroborate to yield 2 moles of silver chloride precipitate, 2 gramequivalents of 1r-allyl palladium ion, and 2 gram equivalents oftetrafluoroborate complex anion.

The resultant anion is stable and is difiicult to coordinate as aligand, accordingly the palladium may promote the reaction together withthe anion and phosphorous compound as active components in the cationicstate. In this case, the precipitate of AgCl is in the catalyst, but itdoes not affect the reaction. Accordingly, it is not always necessary toseparate the precipitate. The process for producing the reaction productof 1,3-conjugated diene compound and the compound having terminal vinylgroup may be carried out by various processes.

For example, the catalyst is fed to an autoclave and an inert gas, suchas nitrogen gas is used to replace the air. The 1,3-conjugated dienecompound and the compound having a terminal vinyl group are further fedto the autoclave and the mixture is reacted by heating.

In the process of this invention, 0.1-10 mole, preferably 1.0-5.0 moleof said compound having a terminal vinyl group to 1 mole of said1,3-conjugated diene compound is used. The amount of catalyst used ispreferably, as palladium in a range of 10- to l0 preferably 10- to 10-parts by weight of said 1,3-conjugated diene compound.

The reaction is usually carried out at l0200 C., prefzerably 50-l50 C.under the pressure of 1-100 kg./ cm.

The process of this invention can be carried out without a solvent.However, the process is usually conducted in the presence of an inertsolvent. The solvent is preferably an aprotic polar solvent, such as ahydrocarbon, e.g., benzene, toluene; substituted hydrocarbons, e.g.,chlorobenzene; ether, e.g., tetrahydrofuran, dioxane; ester, e.g.,methyl acetate, ketone, e.g., acetone. It is also possible to use analiphatic alcohol, e.g., methanol, ethanol, propanol; aromatic alcohol,e.g., benzyl alcohol; cycloaliphatic alcohol, e.g., cyclohexanol; ormulti-valent alcohol, e.g., ethylene glycol.

When the 1,3-conjugated diene compound is oligomerized in the presenceof the alcohol, and the catalyst is prepared by using said phosphorouscompound of tertiary phosphine having at least two saturated aliphatichydrocarbon groups, such as triethylphosphine, tributylphosphine,tricyclohexylphosphine, monophenyl di nbutylphosphine, etc., the dimerand trimer of said 1',4'COI1? jugated diene compound are produced. 1

When the catalyst is prepared without the phosphorous compound or byusing a phosphorous compound other than said phosphorous compound, thealcohol adduct of a chain oligomer such as a dimer and trimer of said1,3- conjugated diene compound is mainly produced with said non-alkoxydimer and trimer.

The various reaction products produced by the process of this inventionare useful as raw materialsfor various synthetic resins and detergents.

Having generally described the invention, a further understanding can beobtained by reference to certain specific examples which are providedherein for purposes of illustration only and are not intended to belimiting in any manner unless otherwise specified.

EXAMPLE 1 0.5 mmole of 1 -methallyl palladium chloride .(1r--C H PdC1 2and 1.0 mmole of tri-n-butylphosphine were dissolved in 40 ml. oftoluene. The solution was fed to a 200 cc. autoclave and 0.47 g. ofbenzene solution of 1.0 mmole of silver tetrafluoroborate AgBF wasadded. After replacing the autoclave with nitrogen gas, 32.5 g. (0.60mole) of butadiene was fed under pressure, and ethylene was further fedto make 44 kg./cm. at 80 C. The mixture was reacted at 80 C. under 44kg./cm. of total pressure for 6 hours.

The autoclave was cooled and excess ethylene was purged and theresultant product was separated by distillation. According to theanalysis of the resultant product by gas chromatography, infraredspectrum, nuclear magnetic resonance spectrum, conversion of butadienewas 76% and the selectivities of the resultant products were as follows:

Percent 3-methyl-l,4-pentadiene 2 1,4-hexadiene 60 2,4-hexadiene 28 C -Ccomponents 4 High boiling products (C up) 4 EXAMPLE 2 0.5 mmole of(7l'-C4HqPdCl) and 1.0 mmole of (n-C H P were dissolved in 40 ml. oftoluene. The solution was fed to a 200 cc. autoclave and 1.0 mmole ofsilver hexafiuorophosphate AgPF was added. After replacing the autoclavewith nitrogen gas, 0.60 mole of butadiene and ethylene were further fedto make 40 kg./cm. at 80 C. The mixture was reacted at 80 C. under 40kg./cm. of total pressure for 8 hours.

The resultant product was separated and analyzed in accordance withthose of Example 1.

The conversion of butadiene was 92% and the selectivities of resultantproducts were as follows:

Percent 3-methyl-1,4-pentadiene 2 1,4-hexadiene 48 2,4-hexadiene 40 C -Ccomponents 4 High boiling products (C up) 2 EXAMPLE 3 Percent3-methyl-l,4-pentadiene 2 1,4-hexadiene 51 2,4-hexadiene 37 EXAMPLE 4 30ml. of chlorobenzene containing 0.5 mmole of (1rC H -PdCl) and 10 mmoleof (n-C H P was mixed with 0.47 g. of benzene solution containing 1.0mmole of AgBF The mixture was used as catalyst and butadiene andethylene were reacted at 80 C. under the pressure of 50 kg/cm. for 5hours, in accordance with the process of Example 3. The conversion ofbutadiene was 70%, and the selectivities of resultant products were asfollows:

Percent 3-methyl-1,4-pentadiene 2 1,4-hexadiene 70 2,4-hexadiene 22 Highboiling products 4 EXAMPLE 5 15 ml. of acetone containing 0.5 mmole of(1rC H PdCl) 2 was mixed with 5 ml. of acetone containing 1.0 mmole ofAgClO The resultant precipitate of AgCl was separated and 1.0 mmole of(n-C H P was added to the of As(C H ClO and the filtrate was distilled.

The resultant product was analyzed in accordance with those ofExample 1. The conversion of butadiene was 96% and the selectivities ofresultant products were as follows:

Percent 3-methyl-l,4-hexadiene 1 1,4-hexadiene 48 2,4-hexadiene 22 C Ccomponents 21 High boiling products (C up) 4 EXAMPLE 6 20 ml. of acetonecontaining 0.5 mmole of (1I'C H7Pdcl) and 1.0 mmole of (n-C H P wasmixed with 0.5 mmole of Ag SiF The mixture was used as catalyst and 0.5mole of butadiene and ethylene were reacted at C. under the pressure of27 kg./cm. for 3 hours. The conversion of butadiene was 30% and theselectivities of resultant products were as follows:

7 EXAMPLE 7 20 ml. of acetone containing 0.5 mmole of bis(benzonitrile)palladium chloride was mixed with 1.0 mmole of AgClO and the precipitateof AgCl was removed and 1.0 mmole of (n-C H P was added to prepare thecatalyst solution.

The catalyst solution and 0.6 mole of butadiene were fed to a 200 cc.autoclave and ethylene was further fed to make 43 kg./cm. at 75 C. Themixture was reacted at 75 C. under the pressure of 43 kg/cm. for 6hours. The resultant product was treated in accordance with the processof Example 5. The conversion of butadiene was 80% and the selectivitiesof resultant products were as follows:

Percent 3-methyl-1,4-pentadiene 1 1,4-hexadiene 68 2,4-hexadiene 19 Highboiling products 5 EXAMPLE 8 Percent 3-methyl-1,4-pentadiene 21,4-hexadiene 23 2,4-hexadiene 59 1,3,6-n-octatriene 11 High boilingproducts 2 EXAMPLE 10 ml. of benzene containing 0.5 mmole of and 1.0mmole of (n-C H P was mixed with 1.0 mmole of AgBF The catalyst solutionthus obtained was used and butadiene and other compounds having terminalvinyl group were reacted in accordance with the process of Example 1.

The conditions and results of the reactions were shown in the Table 1.

TABLE 1 P Buta- Total ercent diene, pressure, Temp., Reaction Conver-Number mole Vinyl compound kgJem. (3. time, hr. sion Selectivity ofproduct 1 0. 6 Propylen 22 90 6 94 n-He tadiene, 27.

isoeptadiene, 23. 1,3,6-n-octatriene, 23. High boiler, 20.

2 0. 2 1-acetoXy-2,7-0ctadiene, 0.2 11101 5 90 6 100Acetoxy-dodecatriene, 43,

1,3,6-n-octatn'ene, 29. High boiler, 20.

N ore-In the experiment No. 2, 20 m1. of benzene was used.

lyst solution. The catalyst solution and 0.6 mole of butadiene were fedin 200 cc. autoclave and ethylene was 'further fed to make 37 kg/cm. oftotal pressure at C. The mixture was reacted at 80 C. under the pressureof 37 kg./cm. for 3 hours.

In the experiment N0. 2, 20 ml. of benzene was used.

EXAMPLE 11 Butadiene and other compounds having a terminal vinyl groupwere reacted with the catalyst of Example 6, in accordance with theprocess of Example 1. The conditions and results of reactions were shownin the Table 2.

TABLE 2 Percent Buta- Total Reaction diene, pressure, Temp., time,Conver- Number mole Vinyl compound kgJem. 0. hr. sion Selectivity ofproduct 1 0.5 Methyl acrylate, 0.5 mol 5 80 6.5 95Mgghy-lfi-heptadienoate,

1, 3, li-n-octatriene, 3. High boiler, 20.

2 0.5 Styrene, 0.5 mol 5 2 100 1-pheny1-1,4-hexadiene,80;

1, 3, ti-n-octatriene, 9. n-Dodecatetraene, 5.

8 0.6 Vinyl acetate, 0.6 mol 6 95 1-acet0 y-,4(2,4).hexadiene, 16. 1, 3,fi-n-octatn'ene, 45. n-Dodecatetraene, 10. High boiler, 20.

1 The styrene was supplied for several times. The conversion ofbutadiene was 98% and the selectivities of the resultant products wereas follows: 65

Percent 3-meth l-14-pentadiene 14 36 32.4 g. (0.30 mole) of1,3,6-n-octatnene containing 2,4-hexadiene 40 70 5 mmole f (1 C H-Pd-Cl) and 1.0 mmole of High boiling products 1 (n-C H P was mixed with1.0 mmole of AgBF in EXAMPLE 9 1.0 mmole of bis(dimethylacetoamide)palladium chloride was dissolved in 20 ml. of isopropanol and 2.0 mmoleof AgPf was added. The precipitate of AgCl was rethe solvent, and themixture was fed in 200 cc. autoclave. Ethylene was further fed underpressure.

The conditions and results of reactions were shown in the Table 3.

TABLE 3"" Reaction" Percent Total Conversion Solvent, pressure, Temp.,Time, of 1,3,5-1'1- Number ml. kg./cm. 0. hr. octatrlene Selectivity ofproduct 1 Benzene, 20. 20 90 5 98 n-Decatriene, 15.

iso-Decatrieue, 15. Isgguers of 1,3,6-n-oetatriene,

2 Ethanol, 42 100 4 100 n-Decatriene, 11.

iso-Decatriene, 13.

Norm-In Experiment 2, AgCl precipitate was removed EXAMPLE 13 0.5 mmoleof (1rC H- PdCl) and 1.0 mmole of tri-n-butyl phosphite were added to0.5 mole of methylacrylate and 1.0 mmole of AgBF was further added toit. The precipitate of AgCl was removed from the resultantmethylacrylate solution. The solution was fed to a 200 cc. autoclave and0.4 mole of butadiene was fed to react them at 75 C. for 6 hours. Theconversion of butadiene was 85%, and the selectivities of resultantproducts were as follows:

. Percent Methylheptadienoate 53 High boiling products 28 EXAMPLE 14Percent Methylheptadienoate 46 l-carbomethoxy-B-cyclohexene- 30 1,3.6-11-oetatriene 9 High boiling products. 8

EXAMPLE 15 1.0 mmole of bis(dimethylacetoamide) palladium chloride, 1.0mmole of '(n-C H P, and 0.2 g. of butadiene were dissolved in ml. ofmethanol and-2.0 mmole of AgBR; was further added. The resultantprecipitate of AgCl was removed from the solution to prepare thecatalyst solution. The catalyst solution and 0.5 mole of butadiene werefed to a 200 cc. autoclave and propylene was further fed to make 22kg./cm. at 90 C. r

The mixture was reacted at 90 C. under the pressure of 22 kg./cn1. for 6hours. The conversion of butadiene from the catalyst solution.

was 84% and the selectivities of resultant products were as follows:

Percent n-Heptadiene 18 Iso-heptadiene 20 l,3,6-n-octatriene l8n-Dodecatetraene 9 High boiling products l9 EXAMPLE 16 1.0 mmole ofbis(dimethylacctoamide) palladium chloride and 1.0 mmole oftri-n-octylphosphine were dissolved in 52 g. of (0.5 mole) of styrene.2.0 mmole of AgBF; was further added to it and the resultant precipitateof AgCl was removed and 1 ml. of methanol was added to the solution toprepare the catalyst solution. The catalyst solution and 0.5 mole ofbutadiene were fed to a 200 cc. autoclave, and were reacted at 85 C. for75 minutes. The conversion of butadiene Was 95%, and the selectivitiesof resultant products were as follows:

Percent l-phenyl-l,4-hexadiene 43 1,3,6-n-octatriene 12 EXAMPLE 17 50.5g. (0.3 mole) of l-acetoxy-2,7-octadiene containing 1:0 mmole ofbis(dimethylacetoamide) palladium chloride was mixed with 20 ml. oft-butanol containing 2.0 mmole of AgBF The resultant precipitate ofAgClwas removed and 1.0 mmole of (n-C H P was added to prepare thecatalyst solution. The catalyst solution and 0.3 mole of butadiene werefed to a 200 cc. autoclave and were reacted at C. for 6 hours. Theconversion of butadiene was 54% and the selectivities of resultantproducts were as follows:

. Percent Acetoxydodecatriene 34 1,3,6-n-octatriene 30 High boilingproducts 20 The following examples relate to oligomerizations of l,

S-butadiene wherein the compound having 1,3-conjugate diene type and thecompound having terminal vinyl group are the same.

EXAMPLE 18 TABLE 4 Reaction Percent Temp., Time, Conversion Number Pcompound 0. hr. of butadiene Selectivities of product,

1 (ll-C4Hp)3P 100 1.5 81 1,3,6-n-oetatriene, 46.

n-Dodecatetraene, 38. n-Hexadecapentaeno, 1. High boiler, 10.

2 (CIH5)3P 100 3 92 1,3,6-n-octatriene,34.

n-Dodecatetraene, 31. n-Hexadecapentacne, 2.

3..:....:-:.:.:. (CoH O)aP 100 8 85 1,3,6-noctatrlene, 29.

n-Dodecatetraene, 24. High boiler, 41.

EXAMPLE 19 The conversion of butadiene was 71%, and the selectivities ofresultant products were as follows:

The catalyst solution was prepared in accordance with Percent theprocess of Example 18 except 1r-allyl palladium chlo- 13,6 n octatriene33 ride (1rC H PdCl) was replaced for 1r-rnethallyl mpodecatetraene 5palladium chloride and n-butyl-diphenylphosphine (I 20 Hi b ili Products24 C H )(C H P was used as phosphorous compound.

The catalyst solution and 1.0 mole of butadiene were fed M T 23 i to a200 cc. autoclave and were reacted at 100 C. for 3 20 ml. of benzenecontalmng 1.0 mole of b1S(b61lZOIllhours. trile) palladium chloride and1.0 mmole of (n-C H P The conversion of butadiene was 90%, and theselectiviwas fed to a 200 cc. autoclave. Further 2.0 mmole of ties ofresultant products were as follows: 25 AgBF and 1.0 mole of butadienewere added and reacted P t at 100 C. for 4 hours. 1,3,6-n-octatriene T eC n ersion of butadiene was 95% and the selectivmDodecatetraene 36 itiesof resultant products were as follows: n-Hexadecapentaene 3 30 PercentHigh boiling products 18 1,3,6-Mwtatr1ene 36 n-Dodecatetraene 34 EXAMPLE20 High boiling products 20 ml. of acetone containing 0.5 mmole of1r-methallyl EX 24 palladium chloride and 1.0 mmole of AgClO was mixed35 with 1.0 mmole of (n-C H P to prepare the catalyst solution. Thecatalyst solution and 1.0 mole of butadiene were fed to a 200 cc.autoclave and were reacted at 100 C. for 5 hours. After the reaction,1.0 mmole of tetraphenylarsonium chloride was added to the resultantproduct to remove ClO; as precipitate As(C H ClO The resultant solutionwas distilled to separate the reaction products. The conversion ofbutadiene was 70% and the selectivities of resultant products were asfollows:

Percent 1,3,6-n-octatriene 51 n-Dodecatetraene 34 High boiling products5 EXAMPLE 21 tivities of resultant products were as follows: a

Percent 1,3,6-n-octatriene 69 n-Dodecatetraene 25 High boiling products3 EXAMPLE 22 20 ml. of tetrahydrofuran containing 1.0 mmole of his(benzonitrile) palladium chloride (C H CN) PdCl;, was mixed with about0.2 g. of butadiene, and then 2.0

mmole of AgBF was added. The resultant precipitate of AgCl was removedand 1.0 mmole of (n-C H P was added. The resultant catalyst solution and1.5 mole of butadiene were fed to a 200 cc. autoclave and were reactedat 10 C. for 6 hours.

0.2 g. of butadiene was dissolved in 40 ml. of acetone containing 0.5mmole of his (dimethyl-acetoamide)palladium chloride and 1.0 mmol. ofAgBE, was added. The resultant precipitate of AgCl was removed and 0.5mmole of (n-C H P was added.

The resultant catalyst solution and 1.0 mole of butadiene were fed to a200 cc. autoclave and were reacted at 100 C. for 5 hours.

The conversion of butadiene was 53%, and the selectivities of resultantproducts were as follows:

Percent 1,3,6-n-octatriene 66 n-Dodecatetraene 22 High boiling products7 The following examples relate to oligomerization of 1,3-butadienewherein various alcohols were respectively used as solvent. When atertiary phosphine having at least two saturated aliphatic hydrocarbongroups'is employed as phosphine compound, the dimer and trimer of 1,3-butadiene were mainly produced. When the other phosphine is employed,the alcohol adduct of the dimer and trimer as well as said dimer of1,3-butadiene, were produced.

EXAMPLE 25 32 g. of methanol containing 2.0 mmole of AgBF was mixed with1.0 mmole of palladium chloride and the mixture was reacted at roomtemperature for 2 hours while stirring. The resultant precipitate ofAgCl was removed and 1.0 mmole of (n-C H P was added.

The resultant catalyst solution and 1.0 mmole of butadiene were fed to a200 cc. autoclave and were reacted at C. for 6 hours.

The conversion of butadiene was 94%, and the selectivities of resultantproducts were as follows:

Percent 1,3,6-n-octatriene 43 n-Dodecatetraene 34 n-Hexadecapentaene 4High boiling products 15 13 EXAMPLE 26 0.5 mmole of wr-methallylpalladium chloride was dissolved in the mixture of 20 ml. of acetone and20 ml. of methanol, and 1.0 mmole of AgB F was further added. Theresultant precipitate of AgCl was removed and 1.0 mmole of (n-C H P wasadded.

The resultant catalyst solution and 1.0 mole of butadiene were fed to a200 cc. autoclave, and were reacted at. 90 C. for 8 hours. Theconversion of butadiene was 96% and the selectivities of resultantproducts were as follows: a

. Percent 1,3,6-n-octatriene 35 n-Dodecatetraene 37 n-Hexadecapentaene 4High boiling products 20 EXAMPLE 27 Thecatalyst solution was prepared inaccordance with the process of Example 25 except 40 ml. of methanolcontaining 2.0 mmole of AgClO was used. The resultant catalyst solutionand 1.0 mole of butadiene were fed to a 200 cc. autoclave and werereacted at 90 C. for 9 hours.

The conversion of butadiene was 85%, and the selectivities ofresultant'products were as follows:

, Percent 1,3,6-n-octatriene 29 n-Dodecatetraene 26 High boilingproducts 20 EXAMPLE 28 1.0 mole of butadiene was reacted at 90 C. for 8hours in the presence of the catalyst solution prepared by adding 1.0mmole of (n-C H P to methanol solution containing 1.0 mmole ofbis(dimethylacetoamide) palladium chloride and 1.0 mmole of Ag SiF Theconversion of butadiene was 62% and the selectivities of resultantproducts were as follows:

. I Percent 1,3,7-n-octatriene 7 1,3,6-n-octatriene 52 n-Dodecatetraene20 High boiling products 3 EXAMPLE 29 -10 mole of butadiene was reactedat 90 C. for 6 hours in the presence of the catalyst solution preparedby adding 2.0 mmole of AgBF to 40 ml. of methanol containing 1.0 mmoleof bis(dimethylformamide) palladium chloride, 1.0 mmole ofmonophenyl-di-n-butylphosphine and 0.3 g. of butadiene, and removing theresultant precipitate of AgCl. The conversion of butadiene was 66%, andthe selectivities of resultant products were as follows:

, Percent 1,3,7-n-octatriene 15 1,3,6-n-oc'tatriene 24 Methoxyoctatriene13 EXAMPLE 30 1.5 mole of butadiene was reacted at 100 C. for 5.5 hoursin the presence of the catalyst prepared by adding about 0.2 g. ofbutadiene to 20 ml. of t-butanol containing 1.0 mmole ofbis(dimethylacetoamide)palladium chloride and then adding 2.0 mmole ofAgBF and removing the resultant precipitate of AgCl and then adding 1.0mmole of (n-C -H P.

The conversion of butadiene was 67%, and the selectivities of resultantproducts were as follows:

I Percent 1,3,6'-n-octatriene' 62 n-Dodecatetraene 28 High boilingproducts 7 EXAMPLE 31 0.1 mole of butadiene was reacted at 80 C. for 6hours in the presence of catalyst solution prepared by adding 1.0 mmoleof triphenylphosphine to 32 g. of methanol containing 0.5 mmole of1r-methallyl palladium chloride and 1.0 mmole of AgBF The conversion ofbutadiene was 91%, and the selectivities of resultant products were asfollows:

' Methoxy-n-hexadecatetraene Percent 1,3,7-n-octatriene 15Methoxy-n-octadiene 42 Methoxy-n-dodecatriene 20Methoxy-n-hexadecatetraene 2 B-methoxy-l-butene 10 EXAMPLE 32 Butadienewas reacted in accordance with the process of Example 31 except 1.0mmole of triphenyl phosphite was used as phosphorous compound and thereaction time was 9 hours. The conversion of butadiene was 64% and theselectivities of resultant products were as follows:

Percent 1,3,7-n-octatriene 31 Methoxy-n-octadiene 36Methoxy-n-dodecatriene 14 Small amount The following examples relate tooligornerization of 1,3-butadiene in the presence of alcohol withoutphosphorous compound for producing alcohol adduct of chain oligomer ofdimer and trimer, and tetramer.

EXAMPLE 33 0.5 mmole of vr-methallyl palladium chloride was dissolved in40 ml. of methanol and 0.5 g. of benzene containing 1.0 mmole of AgBFwas added at room temperature in nitrogen gas atmosphere. The resultantprecipitate of AgCl was removed. The catalyst solution was fed to a 200cc. autoclave and 1.0 mole of butadiene was fed under pressure and wasreacted at 60 C. for 7 hours. The autoclave was cooled after thereaction and unreacted butadiene was recovered, and then the resultantproduct was vacuum distilled to obtain 30 g. of dimer fraction, 17 g. oftrimer and tetramer fraction, 3.3 g. of pentamer and hexamer fractionand 1 g. of high boiling components.

The conversion of butadiene was 77% and the selectivities of resultantproducts were as follows:

Selectivity, Perpercent Ratio cent 1-methoxy-2,7-octadiene 54 {l-adduct97 3-methoxy-1,7 octadiene 3-adduct 3 l-methoxy-n-dodecatriene3-methoxy-n-dodecatriene 3-methoxy-n-hexadecatetraeneMethoxy-n-eicosapentaene Methoxy-n-tetracosahexaene EXAMPLE 34 7 PercentMethoxy-n-octadiene (l-adduct 97%) 66 Methoxy-n-dodecatriene (l-adduct76%) 12 Methoxy-n-hexadecatetraene 16 1 5 EXAMPLE 35 The reaction wasrepeated in accordance with the process of Example 34, except 1.0 mmoleof bis(dimethylformamide) palladium chloride was replaced for 1.2 mmoleof palladium chloride, and the reaction time was 9 hours.

The conversion of butadiene was 70%, and the selectivities of resultantproducts were as follows:

Percent Methoxy-n-octadiene 54 Methoxy-n-dodecatrieneMethoxy-n-hexadecatetraene l8 Methanol adduct of higher oligomer 5EXAMPLE 36 The reaction was repeated in accordance with the process ofExample 35, except bis(dimethylsulfoxide) palladium chloride wasreplaced for bis(dimethylformamide) palladium chloride. The conversionof butadiene was 43% and the selectivities of resultant products were asfollows:

' Percent 1,3,7-n-octatriene 8 Methoxy-n-octadiene 60Methoxy-n-dodecatriene Methoxy-n-hexadecatetraene 7 EXAMPLE 37 1.0 mmoleof palladium chloride was dissolved in 15 ml. of acetone containing 2.0mmole of N-rnethylpyrrolidine and about 0.5 g. of butadiene was furtherdissolved. 1.0 g. of benzene containing 2.0 mmole of AgBF at 80 C. for 6hours. The conversion of butadiene was 78%, and the selectivities ofresultant products were as follows:

Percent Methoxy-n-octadiene 54 Methoxy-n-dodecatriene 4Methoxy-n-hexadecatetraene 22 EXAMPLE 40 Percent Methoxy-n-octadiene(l-adduct 88%) 69 Methoxy-n-dodecatriene (l-adduct 65%) 12Methoxy-n-hexadecatetraene l6 'EXAMPLE 41 0.5 mmoleof r-methallylpalladium chloride and 1.0 mmole of AgBF were dissolved in variousalcohols to prepare catalyst solutions. The catalyst solution and 1.0mole of butadiene were fed to a 200 cc. autoclave and reacted. Theconditions and results of reactions were shown in the Table 5.

TABLE 6 Reaction Percent Temp. Time Conversion N0. Alcohol, mole O ofhr: of butadiene Selectivity 1 Ethanol, 1.0 70 10 44 Ethoxy-n-octadiene,43.

Ethoxy-n-dodeoatriene, 7.

Ethoxy-n-hexadecatetraene, 13.

2 Isopropanol, 0.50-- 60 10 22 Isopropoxy-noctadiene, 65.

Isopropoxy-n-dodecatriene, 9. Isggropoxyn-hexadeeatetraene,

NorE.In Experiment 2, 30 ml. of benzene was used as solvent.

was added to said solution and the resultant precipitate of AgCl andpalladium metal produced by reduction were removed. The resultantcatalyst solution, 10.5 moles of methanol and 1.0 mole of butadiene werefed to a 200 cc. autoclave and were reacted at 80 C. for 8 hours. Theconversion of butadiene was 81% and the selectivities of resultantproducts were as follows:

Percent Methoxy-n-octadiene 30 Methoxy-n-dodecatriene 6Methoxy-n-hexadecatetraene 36 Alcohol adduct of higher oligomer 25EXAMPLE 3 8 Acetone solution containing 1.0 mmole of palladium chlorideand 1.0 mmole of Ag SiF was fed to a 200 cc. autoclave and 0.5 mole ofmethanol and 1.0 mole of butadiene were further fed and reacted at 70 C.for 9 hours.

The conversion of butadiene was 70%, and the selectivities of resultantproducts were as follows Percent Methoxy-n-octadiene 56Methoxy-n-dodecatriene 9 Methoxy-n-hexadecatetraene -3 23 EXAMPLE 39 0.5mole of methanol solution containing 0.5 mmole of palladium chloride,1.0 mmole of AgBF and 200 mmole of dimethylformamide was fed to a 200cc. autoclave and 1.0 mole of butadiene 'was fed in it and reacted Whatis claimed as new and desired to be secured by Letters Patent of theUnited States is:

1. In a process for producing an unsaturated addition product of aconjugated diene compound and a compound having a terminal vinyl groupwhich comprises reacting a conjugated diene compound having the generalformula of:

wherein each R is the same or different and each represents hydrogen, oran alkyl group; and R represents hydrogen, alkyl or an alkenyl group,with a compound hav: ing a terminal vinyl group and having the generalformula of:

17 pound selected from the group consisting of a tertiary phosphinehaving the general formula of:

PRIRII RIII wherein R, R", and R are the same or difierent and eachrepresents alkyl, cycloalkyl or aryl group, and a tertiary phosphitehaving the general formula of:

wherein the definition of R, R and R is the same as the abovedefinition.

2. A process of claim 1 wherein the complex of palladium is anintermolecular complex, a palladium chloride complex having neutralligand or a 1r-a1lyl type palladium chloride.

3. A process of claim 1 wherein the compound having tetraorhexa-fluoro-complex anion or perchlorate anion is a silver salt of saidanion.

4. A process of claim 1 wherein the reaction temperature is between and200 C.

5. A process of claim 2 wherein the palladium complex is 1r-allylpalladium chloride, qr-methallyl palladium chloride, l-methyl-vr-allylpalladium chloride, his(benzonitrile)palladium chloride,bis(dimethylacetoamide)palladium chloride or bis(dimethylformamide)palladium chloride.

6. A process of claim 1 wherein the compound (2) is AgBF AgP F Ag SiF orAgClO 7. A process of claim 1 wherein the phosphorous compound istri-n-hutylphosphine, tri-n-octylphosphine, triphenylphosphine,diphenyl-n-butylphosphine, tri-n-butyl phosphite, or triphenylphosphite.

8. A process of claim 1 wherein an aprotic polar solvent is used as asolvent.

9. The process of claim 1 wherein said reaction is conducted in thepresence of an alcohol and wherein said phosphorous compound is atertiary phosphine containing at least two saturated hydrocarbons of analkyl or cycloalkyl group.

10. A process of claim 9 wherein said phosphorous compound istri-n-butylphosphine or di-n-butylmonophenylphosphine.

B1. A process of claim 9 wherein said alcohol is selected from the groupconsisting of methanol, ethanol, isopropanol, n-butanol or isobutanol.

12. The process of claim 1 wherein R represents Iii;

so as to form a conjugated diene compound having a terminal vinyl groupwherein the definitions of R and R are the same as the above definition,and wherein the reaction product is a chain oligomer or co-oligomer.

13. A process of claim 12 wherein the conjugated diene compound and thecompound having a terminal vinyl group are 1,3-butadiene and isoprenerespectively.

14. The process of claim 1 wherein said compound having a terminal vinylcompound is an a-mOIIOOlBfiD. and wherein the reaction product is aco-dimer.

15. A process of claim 14 wherein said 1,3-conjugated diene compound is1,3-butadiene, and said a-monoolefin having a terminal vinyl group isethylene or propylene.

16. A process of claim 14 wherein the conjugated diene compound is1,3,6-n-octatriene and said compound having a terminal vinyl group isethylene.

References Cited UNITED STATES PATENTS 8/1968 Medema 260-429 10/ 1970Bryant et a1. 260-497 US. Cl. X.R. 260-666 B, 68.0 R

